An Iminosemiquinone-Coordinated Oxidovanadium(V) Complex: A Combined Experimental and Computational Study

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F17%3A00477567" target="_blank" >RIV/61388963:_____/17:00477567 - isvavai.cz</a>

Výsledek na webu

<a href="http://dx.doi.org/10.1021/acs.inorgchem.7b00789" target="_blank" >http://dx.doi.org/10.1021/acs.inorgchem.7b00789</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.7b00789" target="_blank" >10.1021/acs.inorgchem.7b00789</a>

Jazyk výsledku

angličtina

Název v původním jazyce

An Iminosemiquinone-Coordinated Oxidovanadium(V) Complex: A Combined Experimental and Computational Study

Popis výsledku v původním jazyce

Ligand H(4)Sar((AP/AP)) contained two terminal amidophenolate units that were connected by a disulfane bridge. The ligand reacted with VOSO4 center dot 5H(2)O in the presence of Et3N under air and provided a mononuclear octahedral oxidovanadium complex (1). X-ray crystal structure analysis of complex 1 revealed that the oxidation state of the V ion was V and the VO3+ unit was coordinated to an iminosemiquinone radical anion. An isotopic signal at g = 1.998 in the X-band electron paramagnetic resonance (EPR) spectrum and the solution magnetic moment mu(eff) = 1.98 mu(B) at 298 K also supported the composition. The formation of complex 1 preceded through the initial generation of a diamagnetic VO2+-iminoisemiquinone species, as established by time-dependent UV-vis-near-IR (NIR), X-band EPR, and density functional theory studies. The UV-vis-NIR spectrum of complex 1 consisted of four ligand-to-metal charge-transfer transitions in the visible region, while an intervalence ligand-to-ligand charge transfer appeared at 1162 rim. The cyclic voltammogram of the complex showed four oxidation waves and one reduction wave. Spectroelectrochemical studies at fixed potentials revealed that the oxidation and reduction processes were ligand-based.

Název v anglickém jazyce

An Iminosemiquinone-Coordinated Oxidovanadium(V) Complex: A Combined Experimental and Computational Study

Popis výsledku anglicky

Ligand H(4)Sar((AP/AP)) contained two terminal amidophenolate units that were connected by a disulfane bridge. The ligand reacted with VOSO4 center dot 5H(2)O in the presence of Et3N under air and provided a mononuclear octahedral oxidovanadium complex (1). X-ray crystal structure analysis of complex 1 revealed that the oxidation state of the V ion was V and the VO3+ unit was coordinated to an iminosemiquinone radical anion. An isotopic signal at g = 1.998 in the X-band electron paramagnetic resonance (EPR) spectrum and the solution magnetic moment mu(eff) = 1.98 mu(B) at 298 K also supported the composition. The formation of complex 1 preceded through the initial generation of a diamagnetic VO2+-iminoisemiquinone species, as established by time-dependent UV-vis-near-IR (NIR), X-band EPR, and density functional theory studies. The UV-vis-NIR spectrum of complex 1 consisted of four ligand-to-metal charge-transfer transitions in the visible region, while an intervalence ligand-to-ligand charge transfer appeared at 1162 rim. The cyclic voltammogram of the complex showed four oxidation waves and one reduction wave. Spectroelectrochemical studies at fixed potentials revealed that the oxidation and reduction processes were ligand-based.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2017

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

—

Svazek periodika

56

Číslo periodika v rámci svazku

14

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

10

Strana od-do

8068-8077

Kód UT WoS článku

000405972200051

EID výsledku v databázi Scopus

2-s2.0-85024369895